Imido polyphenyl oxides and lubricants containing same

ABSTRACT

This invention provides compounds having a diphenyl ether or a polyphenyl ether moiety between terminal imide structures, as well as lubricant compositions containing same. The new compounds impart extreme pressure, detergency, and antioxidant properties to the lubricant.

I Unlted States Patent 1111 3,622,514

[72] Inventors Joseph John Dickert, Jr. 56] References Cited Lower Makefield Township, Bucks County, UNITED STATES PATENTS 3,037,051 5/1962 Stromber 252/515 A x Tmmsmp, 3,154,560 l0/l964 Osuch 252/51.5 A x [211 App! No gg g 3,169,926 2/1965 Symon 252/51.5 A

. Filed Sept. 1969 3,505,227 4/1970 Lowe 252/5l.5 A [45] Patented Nov. 23, 1971 Primary Examiner-Daniel E. Wyman [73] A i M bil ()fl c ti Assistant Examiner-W. Cannon Attorneys-Oswald G. Hayes, Andrew L. Gaboriault,

Raymond W. Barclay and Claude E. Setliff [54] IMIDO POLYPHENYL OXIDES AND LUBRICANTS CONTAINING SAME 9 Cl i N D i ABSTRACT: This invention provides compounds having a diphenyl ether or a polyphenyl ether moiety between terminal [52] US. Cl 252/47.5, imide mamas, as we" as lubricant compositions containing 252/5 260/326 S same. The new compounds impart extreme pressure, deter- [51] Int. g y and antioxidant properties to the lubricant ClOm H36 [50] Field of Search 252/5 1 .5 A,

IMlDO POLYPI'IENYL OXIDES AND LUBRICANTS CONTAINING SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a new class of compounds and to the use thereof in lubricant compositions to impart extreme pressure, detergency and antioxidant properties thereto. More particularly, the new class of compounds have a diphenyl ether or a polyphenyl ether moiety between terminal imido structures.

2. Summary of the Prior Art It is known that sliding or rubbing metal or other solid surfaces are subject to wear under conditions of extreme pressure. Wearing is particularly acute in modern engines in which high temperatures and contact pressures are prevalent. Under such conditions, severe erosion of metal surfaces can take place, even with lubricants of ever-increasing sophistication, in the absence of load carrying additives. As a consequence, much effort has been expended in discovering additives useful in preventing such wear.

With certain metals, and under certain conditions, particularly high-temperature conditions, many of the conventional additives can cause chemical corrosion. It is contemplated that the compounds of the present invention will cause little, if any such corrosion.

SUMMARY OF THE INVENTION In accordance with the invention, there are provided compounds of the formula R is selected from the group consisting of ethylene, propylene, cycloalkylene of from about three to about six carbon atoms, the alkyl-substituted derivatives thereof, wherein the substituent contains from two to about 200 carbon atoms, arylene having from six to about 10 carbon atoms, and substituted arylene, wherein the substituent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, halo (e.g., chlorine, bromine, iodine, fluorine), hydroxy and mercapto and wherein the said substituents have from six to about 30 carbon atoms;

R"is selected from the group consisting of hydrocarbylene of from one to about 10 carbon atoms and the substituted members thereof, wherein the substituent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, halo, hydroxy and mercapto and wherein the said substituents have from six to about 30 carbon atoms;

n is an integer of from to about q is an integer of from 0 to about 50; and

M is selected from the group consisting of oxygen, sulfur,

selenium and tellurium.

It will be understood with respect to R above, that hydrocarbylene is meant to include CH,-- groups, cycloalkylene groups of from three to about six carbon atoms and arylene groups.

There are also provided lubricant compositions comprising a major amount of a lubricating oil and a minor amount sufficient to provide extreme pressure properties thereto of a compound as described above.

PREPARATION OF THE COMPOUNDS AND SCOPE In general, the compounds may be prepared by any known means. For example, the diphenyl oxide derivatives may be The polyphenyl oxide, as well as compounds containing other bridging elements such as sulfur, can be similarly prepared.

In addition, the appropriate imide may be reacted with a chloroalkyldiphenyl oxide, substantially as follows:

In the above, as has already been stated, the R group may have substituted thereon an alkyl group of from two to about 200 carbon atoms. Preferably the hydrocarbyl will contain from about 16 to about carbons. Such alkyl groups may be placed in the molecule by any appropriate means. In the case of maleic anhydride. this can be done by reacting an olefin therewith. These olefins may be derived from monomers, i.e., ethylene, propylene, butylene, octene, dodecene, hexadecene, or the like. They may also be derived from polyolefins, such as polypropylene, polybutylene, and the like.

Useful anhydrides include those derived from dibasic acids such as succinic and glutaric acids. Also included are the dibasic acid anhydrides having a phenyl, naphthyl or anthryl nucleus in the molecule, as well as the substituted members of such aromatic diacids.

As has already been indicated, the scope of the phenyl portion is not limited to diphenyl oxide derivatives. The portion may, of course, be derived from diphenyl oxide, diphenyl selenide, or the like, but the compounds of the invention include in their scope also those having a plurality of units therein.

The lubricants which are improved by the new compounds of this invention include hydrocarbon mineral oil, either paraffinic or naphthenic, or one of the synthetic lubricating fluids. Such synthetic fluids include polyolefins, polyalkylene monocarboxylic acids, and tetraesters obtained from pentaerythritol and monocarboxylic acids, the acids having from one to about 30 carbon atoms, or mixtures of such acids. In addition, solid lubricants, i.e., greases, capable of being compounded may also be used as the base media in this invention.

The following illustrative examples are intended to describe the invention more fully, and are not to be construed as limitations thereon. All parts, weights and percentages are by weight unless otherwise noted.

EXAMPLEl Preparation of 4,4'-Di-C-n-Hexadecylsuccinimidodiphenyl oxide i n-CmHgaOH-C A mixture of about 32.4 parts (0.1 mole) of n-hexadecyl succinic anhydride, about 10.0 parts (0.05 mole) of 4,4'- diaminodiphenyl oxide and about 200 milliliters of N,N- dimethylformamide was placed in a reaction flask, stirred and heated at reflux temperature (143-l45 C.). for about 6 hours. The mixture was cooled to O5 C. and the precipitated solid isolated by vacuum filtration, washed with distilled water and dried in a vacuum desiccator. The melting point of the crude product was 70-73 C. A small amount of product was recrystallized from an ethanol-water solution, then from methanol. After further purification of the product, the melting point was 76.579 C.

Analysis: Calculated from C l-180N C, 76.80%; H, 9.92%; N, 3.44% Foundic 774.0275H, 9.62%; N, 3.81%.

EXAMPLE 2 About 60 parts (0.1 mole) of polypropylsuccinic anhydride,

about parts (0.05 mole) of 4,4'-diaminodiphenyl oxide and I about 250 milliliters of N,N-dimethylformamide were placed in a reaction flask, stirred and heated to reflux temperature (about 143 C.) for about 6 hours, then allowed to cool to room temperature. The mixture was warmed in a steam bath,- transferred to a beaker and mixed with 800 milliliters of distilled water. Two layers formed, the top layer being a dark brown gel. After stirring at room temperature for about 1 hour, the gel became a solid resinlike material. This material was separated and washed with water.

The product was stirred with warm water and the water decanted, three times, then stirred with warm ethanol, which was also decanted, three times. Benzene was then added to the product and the mixture stirred and heated on a steam bath in a flask equipped with a Dean-Stark trap to remove traces of water and ethanol. The benzene was substantially removed by distillation at steam bath temperature and complete removal was accomplished under reduced pressure. This procedure yielded parts of a product containing 79.81% C, 1 1.42% H, 2.02% N and 5.99% 0.

EXAMPLE 3 Preparation of 4,4'-Diphtha1imidomethyldiphenyl Oxide A mixture of about 29.4 parts (0.2 mole) of phthalimide, about 15.2 parts (0.11 mole) of anhydrous potassium carbonate, about 27.6 parts (0.1 mole) of 4,4'-dichloromethyldiphenyl oxide and about 200 milliliters of N,N-dimethylformamide was placed in a reaction flask, stirred and heated at reflux temperature (about 148 C.) for about 6 hours. The product was washed once with N,N-dimethylformamide twice with water. The damp solid (38 parts) was placed in a vacuum over at 60 C. for about 30 hours, at which time the melting point was 25l256 C. This sample was digested in hot benzene, cooled and recovered by vacuum filtration and recrystallized from N,N-dimethylformamide to give the product melting at 269.5270 C. The analysis is shown below.

Calculated (for C l'l N s) Found:

H, 4.13%; N, 5.73% H, 4.38%; N, 5.98%.

A mixture of about 19.8 parts (0.2 mole) of succinimide, 15.2 parts (0.11 mole) potassium carbonate, 26.7 parts (0.1 mole) of 4,4'-dichloromethyldiphenyl oxide and 200 milliliters of N, N-dimethylformamide was stirred and heated to reflux temperature (about 145 C.) for about 6 hours. The solution was cooled to room temperature, was filtered, and the filtrate was diluted with about 500 milliliters of water. This solution was extracted three times, each time with about 200 milliliters of benzene. The benzene solution was filtered and dried over anhydrous sodium sulfate. The drying agent was removed by filtration and the solvent was removed by vacuum distillation on a steam bath. 30.9 Parts of brown liquid product was obtained having the following analysis:

Analysis found: C, 71.60%; H, 5.99%; N, 5.77%.

EXAMPLE 5 'Preparation of 4,4-Di-C-Polypropylsuccinimidomethyldiphenyl Oxide O R CH- /N-CH2 O R 0361173 H (H3 About 120 parts (0.2 mole) of polypropylsuccinic anhydride (molecular weight of about 600) was mixed with about 1 liter of reagent grade toluene. The mixture was stirred and warmed on a steam bath to effect solution. While stirring continued, the mixture was cooled (ice water bath) to about 3 C. Anhydrous ammonia was passed over the surface of the cooled, stirred mixture until no more heat was evolved (about 3 hours). The toluene was removed by distillation and the mixture was heated under vacuum at 280300 C. for about 4 hours. 114 Parts of product was obtained having 80.92% C, 12.34% H, 1.06% N, and 5.39% 0.

About 60 parts of the above product, about 13.4 parts of chloromethyldiphenyl oxide, about 16.6 parts of reagent grade potassium carbonate and about 300 milliliters of N,N- dimethylformamide were stirred and heated at reflux temperature (about 145 C.) for about 4 hours. The mixture was allowed to cool to room temperature, chilled in an ice bath, and the solvent layer decanted off a viscous insoluble lower layer (product). About 400 milliliters of benzene was added to this product, stirred and warmed on a steam bath to effect solution and filtered. The benzene was removed by vacuum distillation on a steam bath. The product was stirred two times with ethanol, decanting the ethanol each time, and two times with water. also decanting the water each time. The product was then dissolved in benzene and the solution washed by shaking with water. The final traces of water were removed by azeotropic distillation with the benzene. The benzene was finally removed by vacuum distillation.

Analysis found: C, 110.08%;

EXAMPLE 6 Preparation of 4,4'-Di-C-Polybutenylsuccinimidomethyldiphenyl Oxide A mixture of about 127.5 parts (about 0.05 mole) of a polybutenylsuccinimide (molecular weight about 2550), about 6.7 parts (0.025 mole) of dichloromethyldiphenyl oxide, about 8.3 parts (0.06 mole) of potassium carbonate, and 300 milliliters of N,N-dimethylformamide was stirred and heated at reflux temperature (about 148 C.) for about 3 hours. The mixture was cooled and the dark supernatant liquid was decanted off the sludge (a viscous insoluble liquid) in the bottom of the reaction flask. The sludge was dissolved in 250-300 ml. of benzene and filtered. The benzene was removed by distillation at 90-100 C. giving 122 grams of product having the following analysis:

EXAMPLE 7 Found: 0. 2.92%.

m-Bis[p-(C-n-Hexadecylsuccinimido)phenoxy1Benzene ll cnu cn- (2431101133,

I of the product after recrystallization from ethanol-acetone 'was 98-l0l C. The product had the following analysis:

Calculated (for C H N,0,,): C, 76.95%; H. 9.35%; N, 3.09%.

Found: C. 76.86%; H, 9.31%; N, 3.02%.

EVALUATION OF PRODUCTS F our-Ball Wear Test In this test, three steel balls of 52100 steel are held in a ball cup. A fourth ball positioned on a rotatable axis is brought into contact with the three balls and is rotated against them. The force with which the rotatable ball is held against the three stationary balls may be varied according to the desired load. The test lubricant is added to the ball cup and acts as a lubricant for the rotation. At the and of the test, the steel balls are investigated for wear scar; the extent of scaring represents the effectiveness of the lubricant as an antiwear agent. The results shown in table 11 were obtained using 2.4 percent by weight of the compound. The tests were carried out at 200 F. for 30 minutes, under a load of 40 kg. and at a rotational speed of 600 r.p.m.

Pin-On-Disk Wear Test In this test, a stationary pin having a hemispherical tip is held upright against an axially mounted rotatable disk 7.6 cm. in diameter. The disk can be rotated at a constant velocity. The pin describes a circle on the surface of the disk concentric with the axis thereof. Both pin and disk are submerged in a vessel holding the test lubricant so that the point of contact between the pin and the rotating disk is lubricated at all times. The force of the disk against the pin may be changed by varying a load outside of the lubricant vessel. The pin and disk used in the following tests were A151 1018 steel and A181 1020 steel, respectively. The results shown in Table l were obtained at a load of 8 kg. and a sliding velocity of 10 cm./sec. The tests were carried out at 200 F. over a 5-hour period.

The evaluation for the wear rate is reported in units of cc./cm., that is, volume of metal worn away from the pin per distance traveled by the pin.

The lubricants used in the above tests are identified as follows:

Designation Fluid A n-hexndecane B polyphenyl ether C decene trirner TABLE I.PIN-ON-DISK WEAR (1.1100 Mole/ Wear rate, Compound of example g. of A g. of A ecJcm.

4. 7X10'" .1. 6X10" .1. 6X10 None 250,000X10 Zinc, 0,0-dilsogropy1- phosphorodlt loato 0 375 00076 181))(10- IABLE 1I.-FOUR-BALL WEAR DATA Compound Base Wear rah, of example fluid f(avg.) cc./cn1.

None..... 0.15 19 10"" 0. 14 1. 9X10 0. 094 4. 5X10 0.066 5. 2X10-' 0. 098 5. 2X10 0. 079 0.113))(10' 0. 15 .10X10' (l. 18 21)(10' 0. 13 2. 8X10'" 0. 081) 4. 4X10" 0. 10 1. 0X10 Friction.

. v 7 Although the Present invention has been described with I amma preferred embodiments, it is to be understood that modifica- CH? tions andvariations may be resorted to, without departing from the spirit and scope of this invention, as those skilled in and n is the art will readily understand. Variations such as structures in 5 4, Th iti f l i 2 herei i the p nd R i which an imido group is attached to only one end of a polyphenyl ether or in which the imido groups are in a chain Y G M1 fi or incorporated into a polymer structure are examples. i v a We claim: i ll;

l. A lubricating composition comprising a major proportion l of a lubricating oil and a minor proportion of a compound of d n i the formula 5. The composition of claim 2 wherein the compound is i r i Q 5 i 0 I I I I r-JJ l l f ctr Fa si t) I q 6. The composition of claim 2 wherein in the compound R is M {It 1 N itg (1 i (mun-on ii (115-- R is -CH,--- and n is l. 7. The composition of claim 2 wherein in the compound R is wherein:

R is selected from the group consisting of ethylene.v

propylene, cycloalkylene of from about three to about six carbon atoms, the alkyl-substituted derivatives thereof; wherein the substituent contains from two to about 200 i v C 1; carbon atoms, arylene having from six to about 10 carboni atoms, and substituted arylene, wherein the substituent isi is and n is L selected from the group consisting of y aryl, aralkyl, 8. The composition of claim 2 wherein in the compound R is alkaryl, halo, hydroxy and mercapto and wherein the saidt substituents have from six to about 30 carbon atoms;

R is selected from the group consisting of hydrocarbylenei of from one to about l0 carbon atoms and the substituted members thereof, wherein the substituent is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, halo," hydroxy and mercapto and wherein the said substituents have from six to about 30 carbon atoms; R' is CH,-- and n is l.

n is an integer of from 0 to about 10; 9. The composition of claim 2 wherein R is q is an integer of from 0 to about 50; and

, M is selected from the group consisting of oxygen, sulfur, l selenium and tellurium. UHF

2. The composition of claim 1 wherein M is oxygen and q is Q U nis0,Misoxygenandqis l.

3. The composition of claim 2 wherein In the compound R IS i I: l i I PC-105O (5/69) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. '3 622,51 Dated November 23, 1971 In nwfls) Joseph J. Dickert, Jr. and Israel J. Heilweil It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In column line 21, "over" should be oven Column 5, line 55 should appear as follows: Found: C, 79.85% H, 12.92%, N, 2.30%; O, 2.92%. In column line 16, 'and" should be end Signed and sealed this 13th day of June 1972.

(SEAL) A'ttest:

EDWARD M.FLETCHER,JR.

ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. The composition of claim 1 wherein M is oxygen and q is
 0. 3. The composition of claim 2 wherein in the compound R is and n is
 0. 4. The composition of claim 2 wherein in tHe compound R is and n is
 0. 5. The composition of claim 2 wherein the compound is
 6. The composition of claim 2 wherein in the compound R is R'' is -CH2- and n is
 1. 7. The composition of claim 2 wherein in the compound R is R'' is -CH2- and n is
 1. 8. The composition of claim 2 wherein in the compound R is R'' is -CH2- and n is
 1. 9. The composition of claim 2 wherein R is n is 0, M is oxygen and q is
 1. 